Dyeing of hair and other keratinous materials



Unit d No Drawing Filed Jan. 17, 1958, Ser. No. 709,479 Claims priority, application France Jan. 22, 1957 I 3 Claims. (Cl. 167-83) This invention relates to the dyeing of hair, including human hair, and other keratinous materials.

It is known to use, for dyeing hair or other keratinous material, triphenols such as 1,2,4-trihydroxybenzene and 2,4,5-trihydroxytoluene. Nevertheless, using these products alone and at room temperature, it has heretofore been possible only to obtaind relatively light shades. To obtain darker shades these compounds have been mixed with: other oxidation dyes already known for hair dyeing, sucliras phenylene-diamines or aminophenols, or with heavy-metal salts' such as iron salts or copper salts. 1.; L..Stoves and H. Burton, Journal of the Society of Dyers and Colourists (1950), vol. 66, pp. 474 to 478, indicate .(p. 477) that 2,4,5-trihydroxytoluene is capable of dyeing, wool in shades from light reddish-brown to dark brown, depending upon whether the solution is adjusted to an acid or an alkaline pH-value, by operating at 90 "C. for l hour. A process for dyeing hair is also known, in which use is made of the 1,2,4-trihydroxy compounds of benzene (which may also contain other s'ubstituents) in the form of their corresponding'1,2,4- triacyl derivatives; such derivatives are saponified a few moments before their application by boiling them in aqueous alcoholic solution in the presence of an excess of an alkaline reactant, such as sodium carbonate. Hence, thesesaponified derivatives are applied in alkaline medium; whatever the method of oxidation employed (simsirable because of the subsequent chemical treatments.

to which the hair may be subjected e.g., permanent waving and bleaching. Similarly, the additionof ammonia or of aminesto the triphenols employed does accelerate the development of the shade, but since the solutions of immediately before or after the application, are not final at the expiry of the treatment period, which is generally ple oxidation in the air or addition of an oxidizing agentc such-as hydrogen peroxide), only fairly light shades are obtained. 1

Another process is known, in which a trihydroxylated compound such as 2,4, 5'-trihydroxytoluene is employed in aqueous solution, which may be thickened to the form of;a creaman d which contains in addition an aliphatic mercaptan; .there.gis added to such solution, at thetime qfifipp icatiqn to the hair, ammonia or a pr1rnary, sec ondary or tertiary amine of the aliphatic or cycloaliphatic series,-or a salt of any of these. The shades thus obtained, after exposure to the air forabout halfan hour and -at a'temperature of'.'3;5-;40 (3., range fromjgolden blond to black, depending upon the particular conditions;

half an hour. On the contrary, they continue to change very slowly, even if the development is accelerated by the application of hydrogen peroxide. I j It isan object of this invention to provide a process whereby it.is possibletodirectly obtain natural, stable and final shades by means of these same trihydroxylated compounds in a very simple manner. More particularly it provides for obtaining, in a very short time, a. substantially permanent pre-selected coloration which is resistant to shampoos and to permanent waving treatments and 'which is compatible with any subsequent treatment of the hair. I

'i According to the present invention a process for dyeing hair and other keratinous material comprises subjectingthe same to the simultaneous action of at least one triphenol of the following general formula:

no -on no -a wherein Rjrepresents a hydrogen orhalo gen atom'or an ing and drying the hair or other material.

The choice ,of thetriph'enol or of the respective pro 5 portions of the 'various triphenols employed in mixture, as also. the choiceof the oxidising agent and-of the impregnation time, depend upon the final shade which it is desired-to obtain. V

The global triphenol concentration of the solution applied to the hair ,or other keratinous material may vary within fairly widelirnits but is preferably between 0.01

mole and 1 mole of triphenol per litre of dyeing solui tion.

oft-the application, always to be effected in alkaline,

m diu t a so mat; a his in bi new M t a u u erl.

The pH-value of the solutions may vary between 1 V lathe-case where the solution employed contains one of thev aforesaid oxidising agents, account should be taken, in selecting the working pH, of the nature of this oxidising agent. Thus, if an alkali metal or ammo-i 5 nium iodate onperiodate. is employed asthe oxidising reactant, it is preferable not to reduce the pH below 3 alcoholic solutions of 1,2,4-trihydroxybenzene or of'2,4,5-

trihydroxytoluene, which may advantageously be adjusted to an acid pH for application to the hair, the shade being thereafter developed on} the hair itself by the addition of analiphatic'o'r araliphatic primary amineor again, if-

tlie dyeing composition alreadycontain's a salt of such .an amine, by the addition'of analkalirie reactant capable ofliberating this ib ase.

The latterlpro'cesses' atford1 a'final shade granging from lightichestnut to medium chestnut in the spaceofabout half'anhour at roomternperature.

Allythese processes have dis dvantages in vaiyiiigdefact give stable and sufficiently dark shadesl'it fis nude 'and' not to employ strong inorganic acids for obtaining low. pH values. The dyeing process according to the inventionmay be carried out in various ways.

Injone preferred method, an

u aqueous or aqueous} alcoholic solution of thetriphenol or of the mixture of triphenols is' prepared, to which theiinorganicoxidiz-Q ,iug agent or agents is or are added at the time of apple The cation to. the hair or other keratinous product.

, pH of the solution may beadjus te'dto the desired value Thus, although the use'of metallic salts, does .in I V and the oxidizing agent, the pH theriresulting simply by the addition of any appropriate reactant. If preferred it is Iev'en'possible to usejthe solution as such that is to 1 1T sa'y,withoutanyothercOnstituent than the'triphenols p 2915.101 9, w e

from the respective proportions of these two constituents.

Whatever the pH at which the operation is carried out,

the solution is preferably left in contact with the hair or other keratinous material for 5-60 minutes and the gair is then briefly rinsed, shampooed, rinsed again and ried.

In this method of carrying out the process, the inorganic oxidizing agent or agents may be introduced into the triphenol solution either in the form of powder or in aqueous solution.

In another method, the process is carried out in two stages, by first applying the solution of the triphenol or triphenols, free from any oxidizing agent, and allowing this solution to remain in contact with the hair or with the product to be dyed for 5-60 minutes in order to complete the impregnation, partly drying the hair, if desired after rinsing with water, and then applying an aqueous solution of the selected oxidizing agent and leaving it in contact for the period necessary for the development of the shade, generally from 5-20 minutes, the hair then being rinsed, shampooed, rinsed again and dried.

If the pH of the triphenol solution applied in the first stage is not adapted to the nature of the oxidizing agent employed or to the desired effect, or if the brief rinsing which has followed this first application has caused the pH on the hair to revert to a higher excessive value, said value may be modified by adding to the solution containing the oxidizing agent an appropriate reactant, for example an organic or inorganic acid, an acid hydrogen salt or a buffer. However, as noted above, if the oxidising agent employed is an iodate or periodate it is preferable not to reduce the pH value below 3 and to avoid the use of strong inorganic acids for obtaining low pH values.

Whatever the pH chosen for the development of the shade and whether the process is carried out in two stages or in only one stage, the concentration of the oxidizing agent in the solution containing it may be comprised between fairly wide limits, depending upon the desired shade and upon the own solubility of the oxidizing agents which may be employed. Generally speaking, the quantity of oxidizing agent to be employed corresponds to about 0.5 to g. per 100 cc. of the triphenol solution employed, whether or not this solution itself contains the oxidizing agent. The volumes of triphenol solution and/ or of oxidizing agent to be employed are based in each case on the bulk of hair to be treated or on the quantity of other keratinous material to be dyed.

The dyeing process of the invention may be carried out not only by means of aqueous solutions as described above, but also by means of creams, pastes or jellies, the adjustment to the required consistency being effected by any conventional method used in hair dyeing.

The following examples will serve to illustrate the invention:

Example I A solution having the following composition is prepared:

G. 1,2,4-trihydroxybenzene 3 Acetic acid 2 Water to make 100 cc.

G. 1,2,4-trihydroxybenzene 4 Acetic acid Water to make 100 cc.

The pH of this solution is 4. At the time of applica tion to human hair, 2 g. of potassium periodate are added thereto. The solution is left'in contact with the hair for 20 minutes, and the hair is then rinsed, shampooed, rinsed again and dried. The shade obtained is light chestnut and has a very natural appearance.

Example III The following composition is employed:

G. 1,2,4-trihydroxy-5-methylbei1zene 4 Water to make cc.

At the time of application, 2 g. of potassium periodate are added thereto. Nearly white live hair is impregnated with this composition, which is allowed to act for 15 minutes. The hair is rinsed, shampooed, rinsed again and dried. A bright violet-tinged mahogany shade is obtained.

Example IV The following solution is prepared:

G. 1,2,4-trihydroxybenzene 3 Acetic acid 2 Water to make 100 cc.

' The following dyeing composition is prepared:

Example V i G. 1,2,4-trihydroxybenzene 2.5 Antaron PC 34 (a commercial amphoteric surfaceactive compound derived from fatty amide) 5 Water and lactic acid to make 100 cc. at pH 3.

At the time of application, 4 g. of sodium iodate are added to this composition. The pH does not vary. After contact for 15 minutes with live, nearly white hair, the hair is briefly rinsed, shampooed, rinsed again and dried. The shade obtained is light chestnut having a golden tinge.

Example VI Example VII A solution having the following composition is prepared:

G. l,2,4-trihydroxybenzene 3 Sodium tartrate 5 Tartaric acid 5 Water to make 100 cc.

At the time of application to the hair, 5 g. of sodium persulphate are added. The pH of this solution is 3. After impregnation of live white hair, on which the solution is allowed to act for 30 minutes, the pH in contact with the hair falls to 2. After rinsing, shampooing, further rinsing and drying, the hair is dyed golden-blond.

'Whilst the invention is of especial importance in relation to the dyeing of human hair it may also be applied, for example, to keratinous materials in the form of fibers, felts, furs and feathers.

What we claim is:

1. A process for dyeing live human hair at room temperature which comprises applying thereto, a freshly prepared aqueous solution containing a triphenol of the general formula HO OH wherein R is selected from the group consisting of by drogen, halogen, alkyl, alkoxy and hydroxyalkyl, said solution being adjusted to a pH value of at most 7 and containing an oxidizing agent selected from the group consisting of alkali metal and ammonium iodates, periodates and persulphates.

2. A process for dyeing live human hair at room temperature which comprises applying thereto, a freshly prepared aqueous solution containing a triphenol of the general formula HO OH 3. A process for dyeing live human hair at room temperature which comprises applying thereto, a freshly prepared aqueous solution containing -a triphenol of the gen: eral formula HO OH HO R wherein R is selected from the group consisting of hydrogen, halogen, alkyl, alkoxy and hydroxyalkyl, said solution being adjusted to a pH value of at least 3 and at most 7 and containing an oxidizing agent selected from the group consisting of alkali metal and ammonium iodates, periodates and presulphates, said solution containing 0.01 mole to 1 mole of said triphenol per litre and 0.5 to 10 grams of said oxidizing agent per cc.

References Cited in the file of this patent UNITED STATES PATENTS 1,663,202 Kritchevsky Mar. 20, 1928 2,733,186 De Byre Jan. 31, 1956 FOREIGN PATENTS I a 745,531 Great Britain Feb. 29, 1956 745,532 Great Britain Feb. 29, 1956 OTHER REFERENCES Burton et al.: I. S. Dyers and Colorists, vol. 66, September 1950, pp. 474-478.

Kass: Am. Perfumer and Aromatics, September 1956, pp. 47-50. 

1. A PROCESS FOR DYEING LIVE HUMAN HAIR AT ROOM TEMPERATURE WHICH COMPRISES APPLYING THERETO, A FRESHLY PREPARED AQUEOUS SOLUTION CONTAINING A TRIPHENOL OF THE GENERAL FORMULA 